Substituted styrene-polyisoprene copolymer



Jan. 11, 1944.

F. J. SODAY SUBSTITUTED STYRENE-POLYISOPRENE COPOLYMERS Filed March 31, 1939 RING SUBSTITUTED MONO- METHYL STYRENE ISOPRENF- (CATALYST) CATALYTICALLY PARTTA uqr POLYMERIZED ISOPR ENE (HEAT mafia CATA LYsfl RESIN PRODUCT POLYMERIZED RING SUBSTITUTED MONO-METHYL STYRENE-POLYISOPRENE Patented Jan. 11, 1944 SUBSTITUTED STYRENE-POLYISOPRENE COPOLYMER Frank J. Soday, Upper The United Gas Impro poratlon of Pennsylva Darby, Pa., as'signor to I1\gement Company, a cor- Application March 31, 1939. Serial No. 265,151 18 Claims. (c1. zoo-86.5)

This invention relates to new compositions of matter and to a method for their preparation.

More particularly, this invention pertains to resins resulting from reacting one or more monomeric ring substituted mono-methyl styrenes with isoprene which has been partially polymerized catalytically. Such material will be referred to herein as partially polymerized isoprene.

It is an object of this invention to provide a new type of synthetic resins. It is a further object of this invention to provide resins having utility in industrial fields, and ing and liquid coating composition fields.

More particularly, it is an object of this invention to provide possessing excellent ant properties. It this invention to may be used with or without plasticizing agents or lubricants. It is a further object of this invention to provide resins adapted to produce a smooth surface pleasing in appearance. A further object of the invention is to provide molding resins with substantially non-shrinking properties.

Still another object of this invention is to provide resins the color of which may be readily controlled and varied.

A still further object of the invention is to provide resins compatible witha wide variety of additive agents such as fillers, decorative constituents, pigments, softening agents, plasticizers, and the like.

Another object of the invention is to provide a process for preparing resins of the above character.

Still other objects will become apparent to those skilled in the art from the following description and illustrative examples.

This invention is based upon the discovery that new synthetic resins having highly desirable properties may be prepared by reacting one or more monomeric ring substituted mono-methyl styrenes with isoprene which has been previously alkali, acid, and water resistis also a particular object of partially polymerizedcatalytically.

The ring substituted mono-methyl styrenes may be represented as follows CH=CH2 (o-Methyl styrene) particularly in the mold-- varnish and lacquer resins CH=CHz (in-Methyl styrene) CH=CH2 provide molding resins which somewhat with change in (p-Methyl styrene) 1 These ring substituted mono-methyl styrenes may be obtained by'the distillation of the light oil from oil gas, as well as from other sources.

By partially polymerized isoprene is meant isoprene which has been subjected to catalytic polymerization conditions suflicient to change its chemical constitution from monomeric isoprene, said polymerization conditions, however, being insuflicient to, render the polymerized material incapable of further reaction.

The properties of the resulting resins also vary polymerization conditions, both with respect to the initial partial polymerization of isoprene and the subsequent polymerization of one or more monomeric ring substituted mono-methyl styrenes, and the partially polymerized isoprene.

For example, the final resins will have increasingly higher greater initial polymerization of th isoprene.

Furthermore, the relative proportions of monomeric ring substituted mono-methyl styrene and partially polymerized isoprene reflect themselves in the properties of the resultant resinous compounds to a large extent. For example, the resin resulting from reacting 60 parts of monomeric para-methyl styrene with 40 parts of partially polymerized isoprene results in a resinous commelting points with increasingly fiuence are the manner in which the initial and final polymerizations are conducted, the concentration and relative purity of the materials un dergoing polymerization, the nature and quantity of catalyst employed, temperature range, reaction time, and the like.

For example, drastic conditions with respect to temperature, concentration of reactants, proportion of catalyst, and reaction time, may result in insoluble polymers or gels instead of the more desirable soluble resins.

The isoprene employed in the preparation of my new resins may be obtained from any suitable source. For instance, isoprene may be obtained by a variety of synthetic methods. It may be obtained from the pyrogenic decomposition of rubber, or it may be obtained by the fractionation of condensates obtained in the manufacture of carburetted water gas, oil gas, refinery gas, or coke oven gas, or from similar sources. Such fractions will be referred to herein generally as light oil isoprene fractions. Fractions obtained in the manufacture of oil gas are particularly preferred.

Hydrocarbon fractions containing from 5 to 100% of isoprene may be successfully used in the production of the herein described partially polymerized isoprene, although, in general, the use of fractions containing from 50 to 100% isoprene is preferred for the production of resins of high quality.

Fractions in which isoprene is the only diolefine present are preferred, although fractions containing a lesser quantity of butadiene, cyclopentadiene or piperylene, or any combination of two or more of these, or similar materials may be employed without departing from the broad concept of the invention.

The same applies to olefines, such as olefines having five carbon atoms.

The accompanying drawing represents a flow sheet of my invention in its broader aspects. As shown thereon, an initial/step comprises catalytically partially polymerizing isoprene. The resulting product and ring substituted monomethyl styrene are thereafter subjected to further polymerization employing heat and/or a catalyst to obtain a product which is my novel polymerized ring substituted mono-methyl styrene-polyisoprene resin having very desirable characteristics for use in various arts.

INITIAL PARTIAL POLYMERIZATION OF ISOPRENE The partial polymerization of isoprene is effected by means of acid-acting metallic halides and particularly acid-acting metallic halide-organic solvent complexes. Examples of such catalysts are given hereinafter.

Although considerable variation is permissible when employing an acid-acting metallic halide or an acid-acting metallic halide-organic solvent complex as catalyst, the polymerizing temperature should rarely exceed 100 C., and preferably should not exceed 70 C.; the concentration of isoprene should rarely exceed 80% by weight of the total solution, and the concentration of catalyst, which is preferably uniformly distributed, should rarely exceed by weight of the isoprene present, although these values are not to be considered as fixed limits.

Two or more of the foregoing catalysts might be employed.

On the other hand, the initial polymerization may be carried out by a combination of heat and catalyst.

The catalytic partial polymerization may be carried out in the liquid state or in the vapor state, or both, and in the presence or absence of solvents.

The partial polymerization of isoprene in a light oil isoprene fraction is illustrated in the following example.

Emample 1 A light oil isoprene fraction obtained in the manufacture of oil gas and containing 63.5% by weight of isoprene, 28.4% by weight of olefines, and 8.1% by weight of parafiin hydrocarbons was employed.

Fifty parts by weight of this isoprene fraction were polymerized by adding to a mixture containing approximately one part by weight of boron trifiuoride-diethyl ether complex and sixty parts by weight of toluene while maintaining the temperature of this mixture Within a range of 1 to 7 C., and agitating during a 6 minute period of addition. Agitation was continued at this temperature for a period of approximately 21 hours after which the catalyst was hydrolyzed by the addition of water. This was followed by approximately 30 minutes of continuous agitation, after which the resultant mixture containing partially polymerized isoprene and unpolymerized constituents was dried, by the addition of a small quantity of lime, with agitation, for a period of approximately 1 hour. All solid extraneous matter was thereafter removed by filtration.

The fraction containing partially polymerized isoprene, in addition to unpolymerized material, was employed in the preparation of a methyl styrene-polyisoprene resin as will be more fully set forth hereinafter in Example 2.

On the other hand, the unpolymerized material may be wholly or partly removed prior to the final polymerization step.

The ring substituted mono-methyl styrenes employed in the production of my new resins may be obtained from any suitable source, and may be in the form of pure or commercially or technically pure ring substituted mono-methyl styrene, or in the form of a solution or a fraction such as obtained from light oil or a mixture of light oil hydrocarbons. The source of light oil may be the same as in the case of the isoprene previously referred to.

Mixtures of monomeric ring substituted monomethyl styrenes also may be reacted with partially polymerized isoprene to give these new resins. The properties of these resins may be varied considerably by a choice of starting materials.

Para-methyl styrene fractions obtained by the distillation of light oil and having boiling ranges between to 180 C. have been satisfactorily employed in the preparation of my para-methyl styrene-polyisoprene resins. Resins having especially desirable properties have been obtained when employing para-methylstyrene fractions having boiling ranges between and 0. Even more desirable properties are secured in the final resins when the para-methyl styrene fractions employed have boiling ranges between 167 and 173 C- A comparable degree of purity. is preferred when using ring substituted monomethyl styrenes other than para-methyl styrene in the preparation of these new resins.

The use of substantially pure ring substituted mono-methyl styrene or mixtures of substantially pure ring substituted mono-methyl styrenes POLYMERIZATION or RING Smas'nru'ran Mono- METHYL SIT/RENE AND PARTIALLY Pozmiuzan Ponnsoram The polymerization of monomeric ring substituted mono-methyl styrene or styrenes and partially polymerized isoprene is preferably carried out by the application of heat, although the reaction may be carried out through the use of catalysts, with or without the application of heat, without departing from the broad concept of the invention.

The polymerization may be carried out in the liquid state or' in the vapor state, or both, and in the presence or absenceof solvents.

When the polymerization of ring substituted mono-methyl styrene or styrenes and partially polymerized isoprene is efiected by the application of heat, a temperature between 50 to 250 C. is preferred. Temperatures between 75 and 200 C. are found to be particularly suitable.

The reaction time may be varied over fairly wide limits, depending upon the extent of the polymerization desired.

The following example illustrates a procedure for the preparation of my new resin.

Example 2 Approximately 160 parts by weight of a paramethyl styrene fraction obtained from light oil and containing approximately 53% para-methyl styrene. was mixed with approximately 73 parts by weight of a partially polymerized isoprene fraction similar to that prepared by the procedure given in Example 1. This mixture was placed in of 2,000 pounds per square inch. The resulting Example 3 A ring substituted mono-methyl styrene-polyisoprene resin having properties making it-very suitable for use in varnishes and lacquers was prepared as follows:

Approximately 18 parts by weight of a paramethyl styrene fraction obtained from light oil and containing approximately 65% para-methyl prene fraction containing 12 parts by weight of polymer prepared as in Example 1. This mixture was placed in a glass bomb and sealed in an atmosphere of nitrogen. The bomb was heated for a period of days at a temperature of approximately 100 rial was removed from the resultant mass by va- C. Unpolymerized mateporization at a temperature of approximately 100 C. and a pressure of 1.0 mm. of mercury absolute. There was obtained a solid resin in quantity equivalent to approximately 11 parts by weight. This resin possessed excellent properties for use as a protective coating for wood. metal, and similar surfaces due to its high alkali, acid, and water resisting properties.

Example 4 An extremely tough molding resin of relatively high melting point was prepared as follows:

isoprene fraction prepared as described in Example 1 was steam distilled to rembve. .unpolymerized material. Five parts by weight of this concentrated partially polymerized isoprene was mixed with approximately parts by weight of para-methyl styrene in the form of a 74.8% light oil fraction. This mixture was placed in a glass bomb and sealed in an atmosphere of nitrogen, after which it was heated for 8 days at a temperature of approximately C., followed by heating for 2 days at a temperature of approximately 145 0. Unpolymerized material was removed from the resultant mass by vaporization ata temperature of approximately 100 C. and a pressure of 1 mm. of mercury, absolute. The resulting resin resembled ivory in appearance. Approximately 99 parts by weight of resin was secured. It had a melting point of 158 C. as determined'by the capillary tube method.

A portion of this resin was molded at a temperature of 200 C. and a pressure of 2,000 pounds per square inch. The mold took a very high polish and imparted a warm sensation to the touch.

Example 5 A mixture of approximately 15 parts by weight of a partially polymerized isoprene fraction, from which all low boiling material had been removed by vaporization at low pressures. and approximately 85 parts by weight of para-methyl styrene in the form of a 74.8% light oil fraction was sealed in a glass bomb in an atmosphere of nitrogen and heated for 6 days at 100 0., followed by heating for four days at 145 C. Unpolymerized material was then removed by vaporization at low pressures. There was thus obtained approximately 95 parts by weight of a solid resin which had a melting point of C., as determined by the capillary tube method.

A sample of this resin was molded at a pressure of 2000 pounds persquare inch and a temperature of 200 C. The mold resembled ivory in appearance, was exceptionally hard and tough and took a very high polish.

Molding resins made in accordance with my invention are characterized not only by hardness, toughness, pleasing appearance, ability to take a high polish, good molding properties, and inert characteristics, but also in imparting a warm and pleasing sensation to the touch. The latter is extremely important in the trade.

My new resins may be prepared in many desirable color combinations. Color may be obtained either naturally or artificially. Natural colors may be secured by varying the source and may be thus obtained.

Resins which are milk-white in color and which resemble ivory in appearance may be prepared be produced by polymerizing mixtures containing pure monomeric ring substituted mono-methyl styrene or styrenes and partially polymerized isoprene.

Artificial colors and color combinations may through the addition to my new resins of suitable chemical compounds.

Coloring materials, such as organic dyes, inorganic dyes, pigments, and lakes, may be added to any one or more of the reactants, or to the reaction mixture at any stage, but preferably prior to complete polymerization.

As a rule organic dyes and other organic coloring bodies produce resins with pastel shades.

The coloring compound may, of course, be added to the unpolymerized .isoprene, and may or may not be supplemented during the secondary polymerization reaction, as desired. Or the coloring compound can be added during the second phase of the reaction.

If desired, the coloring material itself may be prepared in situ by adding the neecssary materials to the polymerization reaction.

As an example, a short list of suitable coloring materials is given in the following table:

Table 1 Mono azo.

Do. 'Irlphenylmetbane.

lriphenylmethanepyroninc. Red Pyronine. Black Diphenylamine.

as to (1) their inertness, (2) their action as catalysts, and (3) their action as inhibitors in order to obtain the desired result. In' this connection, inhibitors may be employed to retard an otherwise too hasty reaction.

A proper choice of polymerizing conditions will enable almost any type of coloring material to be used.

In addition to coloring materials, other additives may be incorporated, such as fillers, of which asbestos, mica, wood flour, cotton linters, and fabric waste are examples.

A decorative filler functioning very much on the order of a coloring material may be added,

with or without other coloring matter. Examples of decorative fillers are pearl essence, flaked mercurous chloride and chitin extracts.

Furthermore, other agents such as mold lubricants, softeners, plasticizers, and the like, may also be added at any stage of the polymerization process.

While the use of heat as a polymerizing agent is preferred when reacting ring substituted monomethyl styrene or styrenes with catalytic partially polymerized isoprene, other polymerizing agents may be employed if desired either with or without the application of heat.

For instance, polymerization catalysts, such as metallic halides, metallic halide-organic solvent complexes, organic peroxides, contact materials, ultra violet light, ultra sonics, mineral acids, mineral acid-organic solvent mixtures, active metals, etc., may be employed.

able.

assume Examples of catalysts which may be employed in. either the initial or final polymerization reaction are acid-acting metallic halides such as for example, aluminum chloride, aluminum bromide, stannic chloride, boron trifluoride, boron trichloride, zinc chloride, ferric chloride and organic solvent complexes of the foregoing metallic halides. Examples of other catalysts which may be employed in the final polymerization are: pinene peroxide, benzoyl peroxide, clay, activated clay, activated carbon, activated alumina, silica gel, fuller's earth, diatomaceous earth, sulfuric acid, phosphoric acid, sulfuric acid-diethylether mixture, sodium and potassium.

Organic solvent complexes of the metalliohalides are formed by adding the halide to the organic solvent followed by stirring. Examples of organic solvents are benzene, toluene, pentene, decene, dlethyl ether, phenyl methyl ether, phenyl ethyl ether, diisopropyl ether etc.

Metallic halide catalysts (including complexes of such metallic halides) are well-known to be distinguished as a class by their tendency to hydrolyze in the presence of water, giving an acid reaction. They are therefore frequently desig- I nated as acid-acting metallic halides." This term includes the boron halides.

The catalyst employed in the initial reaction maybe used as such or in admixture such as with a suitable solvent to form a suspension, solution, or emulsion. A catalyst when employed in the final reaction may be used in similar manner.

Likewise, the reactants may be employed as such or in admixture such as with a suitable solvent, or with additives such as coloring materials etc., referred to above.

In oder to control more closely the speed and uniformity of the reaction, I may slowly add, with thorough agitation, a solution of the reactant or reactants to a suspension or solution of the catalyst in an organic solvent. Or, the catalyst may be added to the reactant or reactants, or to a solution containing the same.

Examples of suitable solvents or diluents for both catalysts and reactants are benzene, toluene, xylene, solvent naphtha, petroleum naphtha, and carbon tetrachloride.

In any event, the addition of one material to the other is preferably accompanied by thorough stirring which is preferably rapid to insure uniiorm distribution of both materials and temperaure.

In addition, the reaction is preferably carried out in apparatus capable of temperature control such as a Jacketted vessel provided with an agitator.

The quantity of catalyst may be varied over a rather wide range in both the initial and the final polymerization reactions, although it is found preferable to employ limited quantities such as from 011% to 10% by weight of reactants present.

In general, when employing catalysts to polymerize ring substituted mono-methyl styrene or styrenes and partially polymerized isoprene, temperatures between -60 and C. are suit- I prefer, however, to use temperatures between 40 and 60 C.

The upper limit of'permissible temperature is largely determined by (1) the concentration of reactants, (2) the concentration of catalyst, and

of the four conditions, namely (1) temperature, (2) concentration of reactants, (3) proportion of catalyst, and (4) reaction time should be reduced until the desired soluble polymer is obtained.

In general, in both the initial and final polymerizations, it is preferred catalyst from the reaction polymerization is obtained.

Metallic halides, metallic halide-organic solvent complexes and organic peroxides may be removed by any suitable means, such as treating the reaction mass'with an alkaline solution followed by thorough washing with water and filtration. Contact materials may be removed from the reaction mass by settling, filtration, or centrifuging, or otherwise.

While in the foregoing description reference has not been expressly made to a change in polymerization agent during any single polymerization step, it is to be understood that a change in polymerization agent during any single polymerization step might be resorted to is desired.

For instance, the initial partial polymerization of isoprene might be carried outin part by the use of a catalyst, the catalyst removed and the partial polymerization completed by the application of heat. On the other hand, heat might be applied initially followed by the use of a catalyst. ready been referred to.

Likewise, the polymerization of monomeric ring substituted mono-methyl styrene or styrenes with partially polymerized isoprene might be affected in part'by the use of heat and completed by the use of a catalyst, or the polymerization might be started by use of a catalyst, the catalyst removed and the polymerization completed by the use of heat. The use of heat and/or catalyst has already been referred to.

Iprefer to carry out both the initial and the final polymerizations in the presence of an inert and preferably non-catalytic gas, such as carbon dioxide, or nitrogen, or in the presence of solvent vapors, or vapors of the reaction mass, or in a vacuum. In general, the exclusion of air or oxygen from the material during thepolymerization process will prevent any possible formation of undesirable compounds, although this step is by no means essential.

Furthermore, while it is preferred to carry out the initial catalytic partial polymerization and the final polymerization with the reactants at least for the most part in the liquid phase, it is to be understood that the reactants mightbe in the gaseous phase or partly in the gaseous phase and partly in the liquid phase.

While any proportion of partially polymerized isoprene to ring substituted mono-methyl sty- Y rene or styrenes may be employed in making my new resin, I prefer in the case of coating compositions to employ between 50 and 99% partially polymerized isoprene on the undiluted basis to between 1 and 50% monomeric ring substituted mono-methyl styrene or styrenes on the undiluted basis.' 60% to 90% partially polymerized isoprene to 40% to 10% monomeric ring substituted mono-methyl styrene or styrenes is veryv suitable.

The resin obtained by polymerizing a mixture containing 80 parts of partially polymerized isoprene to 20 parts of monomeric ring substituted mono-methyl styrene or styre as is excellent.

On the other hand, in the c'a's'e of casting or molding compositions, l'prefertoiemploy between 50% and 99% monomeric ring substituted monoto completely remove mass after the desired The use of both heat and catalyst has a1 methyl styrene or styrenes to between 50% to 1% partially polymerized isoprene on the undiluted basis. 70% to 95% monomeric ring substituted mono-methyl styrene or styrenes to 30% to 5% 5 partially polymerized isoprene is very suitable.

The resin obtained by the polymerization of a mixture containing 90 parts of monomeric ring substituted mono-methyl styrene or styrenes to par of partially polymerized isoprene usually 1 possesses excellent molding properties. In the event of the removal of extraneous materials, such as unpolymerized material from the partially polymerized isoprene, and hydrocarbons of similar boiling point from the monomeric ring substituted mono-methyl styrene or styrenes before their polymerization, a highly superior product is obtained. If desired, a polymerization diluent such as benzene, toluene, etc., may be employed. While when partially polymerized isoprene is present in greater proportion in the reaction mass, the resulting resin is ideally suited to the coating of surfaces in general, such as metal, wood, glass, ceramic substances, etc., and particularly to the coating of metal surfaces, it may be used for any other purposes, for instance, for lacquers generally, for varnishes either alone or in admixture with other resins, for enamels, for paints, for coating compositions generally, or perhaps, if desired, for casting and molding particularly when the spread in proportion of reactants is not too great.

While when monomeric ring substituted monomethyl styrene or styrenes is present in larger proportion in the reaction mass, the resulting resin is ideally suited for casting or molding purresin might be used for coating purposes, particularly if the spread in proportion of reactants is not too great.

Furthermore, while in the case of the catalyst employed in the initial catalytic partial polyluted form, it is to be understood that any other procedure might be followed without departing from the broad concept of the invention. For instance, all of the diluent may be lirst mixed with eitner the catalyst or the reactant, or reactants, leaving the other in concentrated form. Or the larger part or the diluent may be added to one, thus leaving the other relatively concentrated.

On the other hand, both the catalyst and the reactant or reactants might be employed in concentrated form, particularly if the observations herein with respect to (1) proportion of catalyst, (2) temperature, and (3) reaction time are followed.

It will be understood that any other suitable alkali, such as sodium hydroxide, sodium carbonate, sodium bicarbonate, magnesium hydroxide, an amine or other basic substance might be substituted I01 lime in the removal of catalyst, prelerably followed by a non-acidic drying agent such as sodium smphate or soda lime. Both neutralizing and drying is eiiected by lime.

7o Neutralization is preferably followed by filtration, centrifuging or settling to remove extraneous solids.

While I have spoken rather disparagingly of I the insoluble type of resin, this is because it is also generally infusible and, therefore, has few it any important uses at the present time. Should an important use develop for a resin which is insoluble and infusible before use, my process may likewise be used to obtain this material in good yield by employing drastic conditions as to (1) concentration of reactants, (2) concentration of catalyst, (3) temperature, and (4) reaction time.

It is to he understood that while it is preferred to change all or substantially all of the monomeric isoprene to partially polymerized isoprene during the initial polymerization reaction, such initial polymerization may be conducted in such a manner as to polymerize only a part of the isoprene present without departing from the spirit of the invention.

While in' the examples listed, the initial partial polymerization of the isoprene or isoprene fraction is terminated prior to the addition of the monomeric ringsubstituted mono-methyl styrene or styrenes, the reaction can also be carried out by the partial polymerization of the isoprene, the addition of the monomeric ring substituted mono-methyl styrene or styrenes during the course of this reaction, and the completion of the reaction in any desired manner.

Furthermore, while as above particularly described, the catalyst was removed from the partially polymerized isoprene before its co-polymerization with monomeric ring substituted mono-methyl styrene or styrenes, it is to be understood that the co-polymerization may, if desired, be carried forward without first removing such catalyst.

The term ring substituted mono-methyl styrene as used in the claims, and unless otherwise modified; is intended to embrace pure and substantially pure monomeric ring substituted mono-methyl styrene or a mixture of substituted styrenes, commercial and technical grades thereof, and any mixture or fraction in which one -or more monomeric ring substituted monomethyl styrenes is the predominating active material of said mixture or fraction in the polymerization reaction. with partially polymerized isoprene.

The term isoprene as used in the claims, and unless otherwise modified, is intended to embrace pure and substantially pure monomeric isoprene, commercial and technical grades thereof, and any mixture or fraction in which monomeric isoprene is the predominating active material of said mixture or fraction in the partial polymerization thereof.

The term -partially polymerized isoprene as used in the claims, and unless otherwise modified, is intended to embrace isoprene, as defined in the preceding paragraph, which has been subjected to'catalytic polymerization sufficient to change the chemical constitution of at least a part of the monomeric isoprene, said catalytic polymerization, however, being insufficient to render the polymerized isoprene incapable of further reaction.

The term acid-acting metallic. halide catalyst as used in the claims and unless otherwise modified is intended to include within its scope not only acid-acting metallic halides per se, but also complexes thereof such as organic solvent complexes. The term acid acting metallic halide" is likewise intended to include within its scope boron halide as well as complexes thereof.

When percentages of ring-substituted monomethyl styrene and partially polymerized isoprene are expressly recited in the claims, these specific compounds on the undiluted bases, that is irrespective of the presence of other material.

It is to be understood that the above particular description is by way of illustration and that changes, omissions, additions, substitutions, and/or modifications might be made within the scope of the claims without departing from the spirit of the invention which is intended to be limited only w required by the prior art.

I claim:

1. A process comprising polymerizing a light oil ring substituted methyl styrene fraction obtained in the manufacture of oil gas with a light oil isoprene fraction which has been previously partially polymerized catalytically with the aid of an acid-acting metallic'halide catalyst; said light only isoprene fraction having been obtained in the manufacture of oil gas.

2. A synthetic resin comprising the product resulting from. the polymerization of ring substituted mono-methyl styrene with isoprene which has been previously partially polymerized catalytically with the aid of an acid-acting metallic halide catalyst.

3. A synthetic resin comprising the product resulting from the polymerization of a light oil ring substituted methyl styrene fraction in which ring-substituted methyl styrene is the predominating active compound with isoprene which has been previously partially polymerized catalytically with the aid of an acid-acting metallic halide catalyst.

4. A synthetic resin comprising the product resulting from the polymerization of ring substituted mono-methyl styrene with a light oil isoprene fraction which has been previously partially polymerized catalytically with the aid of an acid-acting metallic halide catalyst, said light oil isoprene fraction prior to said partial polymerization containing more isoprene than any other diolefine.

5. A synthetic resin comprising the product resulting from the polymerization of a light oil ring substituted methyl styrene fraction in which ring-substituted methyl styrene is the predominating active compound with a light oil isoprene fraction which has been previously partially polymerized catalytically with the aid of an acid-acting metallic halide catalyst, said light oil isoprene fraction prior to said partial polymerization containing more isoprene than any other diolefine.

6. A new resinous composition for use in liquid coating compositions comprising the product of the polymerization of from 50% to 9.9% isoprene which has been previously partially polymerized catalytically with the aid of an acid-acting metallic halide catalyst with from 1% to 50% ring substituted mono-methyl styrene.

'7. A new resinous composition for use in liquid coating compositions comprising the product of the polymerization of from 60% to isoprene which has been previously partially polymerized catalytically with the aid of an acidacting metallic halide catalyst with from 40% to 10% of ring substituted mono-methyl styrene.

8. A new resinous composition for use in molding compositions comprising the product of the polymerization of from 50% to 99% ring substituted mono-methyl styrene with from 50% to 1% isoprene which has been previously partially 9. A new resinous composition for use in molding compositions comprising the product of the polymerization of from 70% to 95% of ring substituted mono-methyl styrene with from 30% to isoprene which has been previously partially polymerized catalytically with the aid of an acidacting metallic halide catalyst.

10. A molding composition comprising the product resulting from the polymerization of from 50% to 99% highly concentrated ring substituted mono-methyl styrene with from 1% to 50% isoprene which has been previously partially polymerized catalytically with the aid of a acid-acting metallic halide catalyst.

11. A molding ,composition comprising the product resulting from the polymerization of from 50% to 99% highly concentrated ring substituted mono-methyl styrene with from 1% to 50% highly concentrated isoprene which has been previously partially polymerized catalytically with the aid of an acid-acting metallic halide catalyst.

12. A process comprising polymerizing ring substituted mono-methyl styrene with isoprene which has been previously partially polymerized catalytically with the aid of an acid-acting metallic halide catalyst.

13. A process comprising heat polymerizing ring substituted mono-methyl'styrene with isoprene which has been previously partially polymerized catalytically with the aid of an acidacting metallic halide catalyst.

14. A synthetic resincomprising the product resulting from the heat polymerization of monomeric ring substituted mono-methyl styrene with isoprene which has been previously partially polymerized catalytically with the aid of an acidacting metallic halide catalyst.

which has been previously partially polymerizedcatalytically withthe aid of an acid-acting metallic halide catalyst with from to 10% monomeric ring substituted mono-methyl styrene.

16. A new resinous composition comprising the thermoplastic product resulting from the heat polymerization of from to monomeric ring substituted mono-methyl styrene with from 30% to 5% isoprene which has been previously partially polymerized catalytically with the aid of an acid-actingmetallic halide catalyst. I

1'7. A process for the copolymerization of ring substituted mono-methyl styrene and a light oil isoprene fraction at leastv 50% in isoprene concentration, comprising subjecting said light oil isoprene fraction to polymerizing conditions in the presence of an acid-acting metallic halide catalyst and maintaining the temperature throughout the reaction mass not in excess of C., the concentration of isoprene not in excess of 80% by weight, and the proportion of catalyst to isoprene not in excess of 10% by weight, stopping the foregoing reaction while said isoprene is still in a partially polymerized state, admixing resulting partially polymerized isoprene and monomeric ring substituted mono-methyl styrene. and subjecting the resulting admixture to polymerizing conditions-to produce a synthetic resin. Y

18. The product of the process of claim 1'1. I

FRANK J. SODAY. 

